Thermal decomposition of magnesium chloride

ABSTRACT

A method for conversion of magnesium chloride into magnesium oxide and HCl includes the steps of providing a magnesium chloride compound to a thermohydrolysis reactor, the reactor being at a temperature of at least 300° C., withdrawing MgO from the thermohydrolysis reactor in solid form, and withdrawing an HCl containing gas stream from the thermohydrolysis reactor. The magnesium chloride compound provided to the thermohydrolysis reactor may be a solid magnesium chloride compound which comprises at least 60 wt. % of MgCl2.4H2O.

The present application is a continuation application of U.S.application Ser. No. 15/129,431 filed Sep. 27, 2016, which in turn is aU.S. national stage application of PCT/EP2015/056895 filed Mar. 30,2015. Each of these prior applications is incorporated herein byreference in its entirety.

The present invention pertains to a method for conversion of magnesiumchloride into magnesium oxide and HCl. The invention also pertains to amethod for converting a magnesium chloride solution, and to inintegrated process comprising a fermentation step, a separation step,and a step for converting a magnesium chloride solution.

Methods for manufacturing carboxylic acids through fermentation areknown in the art. In these methods, the carboxylic acid is oftenprepared in the form of a salt, e.g. a magnesium salt. Upon recoveringthe carboxylic acid, salt solutions are obtained, which require furtherprocessing.

For example, WO00/17378 describes a method for manufacturing lacticacid, wherein in a fermentation process a magnesium lactate solution isprepared. The magnesium lactate solution is acidified with HCl to yielda solution comprising lactic acid in a magnesium chloride solution. Thelactic acid is recovered from the solution. The resulting magnesiumchloride solution may be processed by subjecting it to athermohydrolysis step at a temperature of at least 500° C. to react themagnesium chloride with water to yield magnesium oxide powder andhydrochloric acid. The heat required for the thermohydrolytic reactionis provided by the in situ combustion of fuel.

WO2013/025106 describes a method for manufacturing carboxylic acidsthrough a process comprising the steps of acidifying a magnesium salt ofa carboxylic acid with HCl to form an acid and a magnesium chloridesolution, and isolating the acid from the solution throughprecipitation. It is indicated that the magnesium chloride solution maybe processed through thermal decomposition.

WO2013/093028 describes a method for manufacturing carboxylic acidsthrough a process comprising the steps of acidifying a magnesium salt ofa carboxylic acid with HCl to form an acid and a magnesium chloridesolution, and isolating the acid from the solution through extractionfollowed by back extraction. It is indicated that the magnesium chloridesolution may be processed through thermal decomposition.

In the references cited above, the magnesium chloride solutions areprocessed by providing the solution to a thermal decomposition step,where the magnesium chloride reacts with water from the solution to formsolid magnesium oxide and a gas stream comprising water and HCl.

Other processes for converting magnesium chloride to magnesium oxidehave also been described.

EP25427 describes spray-drying of a magnesium chloride solution to formmagnesium chloride dihydrate, and roasting the magnesium chloridedihydrate at 600° C. in a rotating oven.

U.S. Pat. No. 4,425,314 also describes conversion of magnesium chloridedihydrate to MgO at a temperature of 600-800° C. The magnesium chloridedihydrate is advantageously obtained by drying an aqueous magnesiumchloride solution to form magnesium chloride hexahydrate, and convertingthe compound into the dihydrate.

DD28740 describes drying of a magnesium chloride solution to formmagnesium chloride dihydrate, e.g. using a spray dryer. The magnesiumchloride dihydrate is then contacted in a reaction chamber at atemperature of at least 800° C. with hot gas.

While the conversion of magnesium chloride dihydrate into magnesiumoxide is believed to form an improvement over the processing ofmagnesium chloride solutions in that a process of improved flexibilityis obtained, it has been found that there is still need for an improvedprocess, in particular a method which can be carried out at higher speedand at lower temperatures than the processes known in the art. Thepresent invention provides such a process.

The invention pertains to a method for conversion of magnesium chlorideinto magnesium oxide and HCl, comprising the steps of

-   -   providing a magnesium chloride compound to a thermohydrolysis        reactor, the reactor being at a temperature of at least 300° C.,    -   withdrawing MgO from the thermohydrolysis reactor in solid form,        and withdrawing a HCl containing gas stream from the        thermohydrolysis reactor, wherein the magnesium chloride        compound provided to the thermohydrolysis reactor is a solid        magnesium chloride compound which comprises at least 50 wt. % of        MgCl2.4H2O.

Surprisingly it has been found that by providing solid magnesiumchloride compound which comprises at least 50 wt. % ofMgCl2.4H2O.hydrate as starting material for the thermohydrolysis, aprocess is obtained which is fast, can be carried out without blockingof the equipment, and can be operated in a manner which is efficientboth as regards apparatus and energy. It can also be integrated in aprocess for converting a magnesium chloride solution.

The present invention will be discussed in more detail below.

The invention will be illustrated by the following figures, withoutbeing limited thereto or there by.

FIG. 1 illustrates a first embodiment of the present invention.

FIG. 2 illustrates a second embodiment of the present invention, whereinthe step of converting a specific magnesium chloride compound tomagnesium oxide and HCl is combined with a step of manufacturing thespecific magnesium chloride compound from a magnesium chloride solution.

FIG. 3 illustrates a third embodiment of the present invention, whereinthe process of FIG. 2 is integrated into a fermentation process.

In the process according to the invention it has been found that theselection of MgCl₂.4H₂O as starting material gives attractive results.In contrast, other solid magnesium chloride compounds are less suitablefor use as starting material for thermohydrolysis. More in particular,magnesium chloride anhydrate and magnesium chloride monohydrate havebeen found to require a long reaction time, higher reactiontemperatures, and the presence of HCl. Magnesium chloride dihydrate alsorequires a relatively long reaction time and higher temperature. On theother hand, magnesium chloride hexahydrate has been found to melt, whichresults in blocking of the equipment.

In the process according to the invention, a solid magnesium chloridecompound comprising at least 50 wt. % of MgCl2.4H2O is provided to athermohydrolysis reactor.

It is preferred for the magnesium chloride compound to comprise lessthan 30 wt. % of magnesium chloride hexahydrate, in particular less than20 wt. %, more in particular less than 10 wt. % and/or less than 40 wt.% of the total of magnesium chloride anhydrate and magnesium chloridemonohydrate, preferably less than 30 wt. %, more preferably less than 20wt. %, still more preferably less than 10 wt. %. It is also preferredfor the magnesium chloride compound to comprise less than 40 wt. % ofthe total of magnesium chloride anhydrate, magnesium chloridemonohydrate, and magnesium chloride dihydrate, preferably less than 30wt. %, more preferably less than 20 wt. %, still more preferably lessthan 10 wt. %. Within this embodiment it is preferred to also meet therequirement on the percentage of magnesium chloride hexahydrate asspecified above.

It is preferred for the magnesium chloride compound to consist for atleast 60 wt. % of MgCl2.4H2O, in particular at least 80 wt. %, more inparticular at least 90 wt. %. This is because MgCl2.4H2O gives bestresults in the conversion into magnesium oxide, requiring lowerconversion temperatures and shorter reaction times.

The composition of the magnesium chloride compound can be determined bymethods known in the art, e.g., via XRD.

In the thermohydrolysis step, the magnesium chloride compound is heatedto a temperature of at least 300° C. The process step is sometimes alsoindicated as the roasting step or thermal decomposition step. In thethermohydrolysis step magnesium chloride reacts with H₂O to form MgO andHCl. MgO is withdrawn from the thermohydrolysis reactor in solid form. AHCl containing gas stream is also withdrawn from the thermohydrolysisreactor.

Thermal decomposition is conducted at a temperature of a least 300° C.,which is the minimum temperature at which MgCl₂ decomposes. Preferably,thermal decomposition is conducted at a temperature of at least 400° C.Due to energy costs, the temperature is preferably below 1000° C., morepreferably below 800° C., in particular below 700° C., more inparticular below 600° C. It has been found that for magnesium chloridetetrahydrate as it is used in the present invention, a high degree ofconversion can be obtained in a temperature range of 300-600° C. whilestill operating at reasonable throughput. Operating in a temperaturerange of 350-550° C., in particular 400-500° C. is considered preferred,as in this temperature range an optimum balance may be obtained betweenthe energy considerations influencing the selection of the temperatureand throughput considerations. The temperature mentioned is thetemperature of the gas in the unit.

Thermal decomposition as applied in the present invention is preferablyconducted at a pressure of 0.1-10 bar. However, the use of elevatedpressure may be undesirable, because of an increased risk of corrosiondue to the HCl not being able to condense. Preferably, thermaldecomposition is conducted at atmospheric pressure, to avoid unnecessaryenergy costs and the need for expensive high pressure equipment.

In the thermal decomposition step, the magnesium chloride tetrahydrateis converted to MgO and HCl. The amount of water of hydration present inthe magnesium chloride hydrate is sufficient to provide the oxygen andhydrogen required for stoichiometric conversion. Nevertheless, it may bepreferred to add a small amount of water during the thermaldecomposition step, as this may help to obtain complete conversion.Suitable amounts of water, if added are, e.g., 0.01-10 wt. %, calculatedon the weight of the magnesium chloride compound.

The thermohydrolysis is generally carried out in the presence of a gasstream provided to the reactor, which can be used to provide heat to thesystem and withdraw HCl from the reactor. The nature of the gas streamis not critical. It can, e.g., be air or a combustion gas. The lattermay be preferred because of its higher temperature.

In one embodiment the gas stream comprises 40-100 wt. % nitrogen gas, inparticular 40-80 wt. % nitrogen, 0-15 wt. % of oxygen, and 0-20 wt. % ofCO2. Water can, e.g., be present in an amount of 5-20 wt. %. Obviously,the total of the composition will amount to 100 wt. %. A suitable gascan, e.g., be a gas stream resulting from a combustion step, e.g., thecombustion of natural gas.

It has been found that the presence of HCl may help to ensure completeconversion within the time frame of the reaction. Not wishing to bebound by theory it is believed that the presence of HCl may help toprevent the formation of MgClOH, which has a low reactivity. As HCl isformed during the reaction, its beneficial presence can be profited fromby leading the product gas over the magnesium chloride compound still tobe converted. If so desired, it is possible to add additional HCl duringthe reaction.

The thermohydrolysis reactor may have any conventional size or shape,and may op operated in continuous mode or batch mode. Where applicablethe gas stream can be co-current with the transport direction of themagnesium chloride compound or countercurrent with the transportdirection of the magnesium chloride compound. In a preferred embodimentthe direction of the gas stream is countercurrent to the transportdirection of the magnesium chloride compound. Suitable thermohydrolysisapparatus is known in the art, and include spray roasters and fluid bedroasters. In the present case, apparatus with a high degree of filling,e.g. 10-50 vol. %, calculated on the internal volume of the unit, can beused for example. An advantage of a relatively high degree of filling isthat temperature and residence time can be controlled quite easily.

In one embodiment, the thermohydrolysis reactor is a tube reactorwherein the magnesium chloride compound enters the reactor at or nearone end of the reactor, further indicated as the feed end, and productmagnesium oxide is withdrawn at or near the other end of the reactor,further indicated as the product end, while a gas stream enters thereactor at or near the product end, and a gas stream comprising HCl iswithdrawn at or near the feed end. This embodiment is preferred becauseit ensures that the product gas is led over the magnesium chloridecompound still to be converted as explained above. It is also attractivebecause it allows an efficient use of energy. Further, tube reactorsallow the use of a relatively high degree of filling, as indicatedabove.

As will be discussed in more detail below, the tube reactor willgenerally be provided with mixing means and/or transportation means.

This embodiment is illustrated in FIG. 1.

In FIG. 1, a tube reactor (1) is depicted, which is at elevatedtemperature through heating means (not shown). The magnesium chloridecompound is provide to the reactor through line (2), where it isconverted into magnesium oxide, which is withdrawn through line (3). Thereactor may comprise transportation means (not shown) for the solidmaterial. Suitable transportation means encompass rotating internalscrews, paddles or discs, or a rotating wall. It is also possible forthe reactor to be at an angle with the horizontal, with the feed endbeing located higher than the product end. The rector can also bevertical, or be provided with a moving bed.

A heated gas stream is provided to the reactor through line (4). The gasstream comes into contact with the solid material, i.e. magnesiumchloride compounds and magnesium oxide, present in the reactor. The HClgenerated during the conversion reaction is taken up by the gas stream,and a HCl containing product stream is removed through line (5).Suitable reactors are known in the art. They include, for example, arotating kiln, a moving bed, or a screw conveyor. It is within the scopeof the skilled person to select a suitable reactor configuration.

In this embodiment, the temperature of the gas stream provided to theunit will decrease over the unit due to heat transfer. It is preferredfor the gas stream removed from the unit to have a temperature of atleast 300° C., in particular at least 400° C. The maximum temperaturemay be at most 1000° C., in particular at most 800° C., more inparticular at most 700° C., in some embodiments at most 600° C. A rangeof 350-550° C., in particular 400-500° C. may be preferred. Thetemperature of the gas stream as it enters the unit will be higher thanthe temperature as it leaves the unit. The exact entrance temperaturewill depend on the source of the gas stream and on the heat transferproperties of the unit. The entrance temperature may be, e.g., in therange of 700-1500° C., in particular 800-1500° C.

It has been found that the process according to the invention makes forefficient conversion of the magnesium chloride compound to magnesiumoxide. This makes for low residence times. In one embodiment, theresidence time in the reactor is at most 30 minutes, calculated fromentrance of the magnesium chloride compound in the reactor to removal ofthe corresponding magnesium oxide from the reactor. Residence time maybe lower, e.g., at most 20 minutes, or at most 15 minutes, or at most 10minutes, or even less, e.g., at most 5 minutes.

Generally, the reaction time will be at least 15 seconds. The exactresidence time will depend on the type of reactor and the processconditions. Residence time can be reduced by selecting a higheroperating temperature, a smaller particle size, and providing additionalwater (steam) or HCl.

The starting material in the present invention is a solid magnesiumchloride compound comprising at least 50 wt. % of MgCl2.4H2O. Asindicated above it is preferred for the magnesium chloride compound toconsists for at least 60 wt. % of MgCl2.4H2O, in particular at least 80wt. %, more in particular at least 90 wt. %.

The magnesium chloride compound comprising at least 50 wt. % ofMgCl2.4H2O can be obtained by drying a magnesium chloride solution undercontrolled conditions, namely at a temperature of 100-160° C. If thedrying is carried out at a temperature below 100° C., magnesium chloridehexahydrate, the presence of which will detrimentally affect theconvention step to MgO, will be formed in too high amounts. For thisreason it may be preferred for the drying to be carried out at atemperature of at least 110° C., in particular at least 120° C. On theother hand, if the drying is carried out at a temperature of above 160°C., magnesium chloride anhydrate, magnesium chloride monohydrate, andmagnesium chloride dihydrate, the presence of which will detrimentallyaffect the convention step to MgO, will be formed in too high amounts.It may be preferred to carry out drying at a temperature of at most 140°C.

It may be preferred for the drying step to be carried out at atemperature of 110-160° C., more specifically 120-160° C. The preferencefor this temperature range is triggered by the desire to form magnesiumchloride tetrahydrate and by energy considerations. It is within thescope of the skilled person to select a suitable drying temperature. Itis noted that the temperature for the drying step as specified here isthe temperature in the dryer.

The concentration of the magnesium chloride starting solution is notcritical, and may depend on what is available. As a general range avalue of 5-45 wt. % may be mentioned. It may be preferred for themagnesium chloride concentration to be relatively high, e.g., in therange of 20-45 wt. %, more in particular in the range of 30-45 wt. %.The use of more concentrated solutions is accompanied by less waterremoval, which is attractive from an economic point of view. Furtheradvantages of the use of higher concentrations in specific embodimentswill be discussed below.

The drying step can be carried out by methods known in the art.Spray-drying is suitable, both from a practical point of view and froman economic point of view. Other methods like fluidized bed drying canalso be used. It is within the scope of the skilled person to determinesuitable drying methods.

In one embodiment, the drying step is carried out in the presence of aHCl-containing gas stream. This will be the case where a HCl-containinggas stream derived from the thermohydrolysis step is provided to thedrying step. This is particularly attractive, because the gas stream isderived from the thermohydrolysis step at a high temperature, e.g., ofat least 300° C., in particular at least 400° C., and the hightemperature can be used to evaporate water. It may be preferred for thegas stream to be at most 1000° C., in particular at most 800° C., morein particular at most 700° C., in some embodiments at most 600° C. Arange of 350-550° C., in particular 400-500° C. may be preferred. It isnoted that where a gas stream with a temperature in this range is usedin spray drying, its temperature will immediately be reduced to a lowervalue, in particular a value within the range of 100-160° C., due to theevaporation of water. In the case of a spray dryer, the dryingtemperature in the unit, which is important for the formation of thedesired type of magnesium chloride hydrate as is discussed above, isdependent on the temperature of the entrance gas and on theconcentration of the magnesium chloride solution, which determines theamount of water to be evaporated. By regulating the temperature of thespray drying gas and the concentration of the magnesium chloridesolution, the drying temperature within the unit can be set at thedesired value.

In one embodiment, the present invention pertains to an integratedprocess for converting a magnesium chloride solution into magnesiumoxide and HCl, which process comprises the steps of

-   -   subjecting a magnesium chloride solution to a drying step at a        temperature of 100-160° C., in particular 120-160° C. to form a        magnesium chloride compound comprising at least 50 wt. % of        MgCl2.4H2O,    -   providing the magnesium chloride compound to a thermohydrolysis        reactor, the reactor being at a temperature of at least 300° C.,        and    -   withdrawing MgO from the thermohydrolysis reactor in solid form,        and withdrawing a HCl containing gas stream from the        thermohydrolysis reactor.

In a preferred embodiment, the drying step is a spray drying step, andthe HCl containing gas stream withdrawn from the thermohydrolysisreactor is provided to the spray drying step to be combined with themagnesium chloride solution. This will be discussed in more detailbelow.

The descriptions of the various aspects of the individual steps as givenabove also apply to the integrated process.

One embodiment of the integrated process is illustrated in FIG. 2.

In FIG. 2, line (6) provides a magnesium chloride solution to a dryer(7). In dryer (7), a solid magnesium chloride compound is formed, whichis provided through line (2) to thermohydrolysis reactor (1). In reactor(1) the magnesium chloride compound is converted into magnesium oxide,which is withdrawn through line (3). A heated gas stream is provided tothe reactor through line (4). The gas stream comes into contact with thesolid material, i.e. magnesium chloride compounds and magnesium oxide,present in the reactor. The HCl generated during the conversion reactionis taken up by the gas stream, and a HCl containing product stream isremoved through line (5). In the embodiment presented in FIG. 2) the HClcontaining gas stream is provided to dryer (7), where the heat in thegas is used in the drying. The dryer (7) generates an off gas, which iswithdrawn through line (8). At least in the case that the effluentstream (5) from reactor (1) is provided to dryer (7), the off gas fromdryer (7) contains HCl, generally in an amount of 5-30 wt. %, inparticular 15 to 30 wt. %, more in particular 20-25 wt. %. The furthercomposition of the off gas is not critical. It will depend on the gasprovided to reactor (1) through line (4). It will generally comprisenitrogen and optionally one or more of oxygen, CO2, and furthercompounds.

The offgas may be processed as desired. In one embodiment, as depictedin FIG. 2, the offgas is provided to an absorber (9), where it iscontacted with water which absorbs the HCl to form a solution of HCl inwater. Depending on the concentration of HCl in the off gas, the HClsolution may have a concentration of 10-30 wt. %, in particular 15-30wt. %, more in particular 20-25 wt. %. These high concentration rangescan in particular be obtained where a magnesium chloride solution with arelatively high concentration is used as starting material for thedrying step. This is a further reason why the use of such moreconcentrated solutions is considered preferred.

As indicated earlier, the process according to the invention isparticularly suitable for incorporation into a method for manufacturingorganic components, in particular carboxylic acids using a fermentationstep.

In one embodiment the present invention therefore pertains to a processcomprising the steps of

-   -   subjecting a carbon source to a fermentation step to form a        carboxylic acid, which fermentation step comprises the steps of        fermenting a carbon source by means of a micro-organism in a        fermentation broth to form carboxylic acid and neutralizing at        least part of the carboxylic acid by adding a magnesium base        selected from magnesium oxide and magnesium hydroxide, thereby        obtaining a magnesium carboxylate,    -   subjecting the magnesium carboxylate to an acidification step        wherein the magnesium carboxylate is contacted with HCl in an        aqueous environment to form an aqueous mixture comprising        carboxylic acid and magnesium chloride,    -   subjecting the aqueous mixture comprising carboxylic acid and        magnesium chloride to a separation step, to form an effluent        comprising carboxylic acid and a magnesium chloride solution,    -   subjecting the magnesium chloride solution to a drying step at a        temperature of 100-160° C., in particular 120-160° C., to form a        magnesium chloride compound comprising at least 50 wt. % of        MgCl2.4H2O,    -   providing the magnesium chloride compound to a thermohydrolysis        reactor, the reactor being at a temperature of at least 300° C.,    -   withdrawing MgO from the thermohydrolysis reactor in solid form,    -   withdrawing a HCl containing gas stream from the        thermohydrolysis reactor.

In a preferred embodiment of this integrated process, the magnesiumoxide withdrawn from the thermohydrolysis reactor is recycled at leastin part to the fermentation step. This can be done in the form of MgO orafter conversion into magnesium hydroxide, e.g., by contacting themagnesium oxide with water to obtain a magnesium hydroxide slurry.

In a preferred embodiment of the integrated process, the HCl-containinggas stream derived from the drying step is recycled at least in part tothe acidification step. In one embodiment the HCl-containing gas streamis converted to a HCl solution by absorbing it in water, and thesolution is recycled to the acidification step. In another embodiment,the HCl-containing gas stream is provided to the acidification step ingaseous form.

It is particularly preferred for the integrated process according to theinvention to encompass a combination of the MgO recycling and the HClrecycling described above.

The specific embodiments and preferences described above for the processaccording to the invention also apply to the integrated process.

The various steps in the integrated process which are additional to theprocessing of the magnesium chloride solution will be discussed below.

In the first step a carbon source is subjected to a fermentation step toform a carboxylic acid, which fermentation step comprises the steps offermenting a carbon source by means of a micro-organism in afermentation broth to form carboxylic acid and neutralizing at leastpart of the carboxylic acid by adding a magnesium base selected frommagnesium oxide and magnesium hydroxide, thereby obtaining a magnesiumcarboxylate.

Fermentation processes for the manufacture of carboxylic acids are knownin the art and require no further elucidation here. It is within thescope of the skilled person to select, using his common generalknowledge, a suitable fermentation process, depending on the desiredacid to be produced, the carbon source and the microorganism available.

The product of the fermentation process is a fermentation broth, whichis an aqueous liquid comprising magnesium carboxylate, biomass, andoptionally further components such as impurities like are sugars,proteins, and salts.

If so desired, the fermentation broth may be subjected to a biomassremoval step, e.g., a filtration step, before further processing. Thisis generally preferred for improving product quality. Depending on thecarboxylic acid produced, another intermediate step may be separation ofsolid reaction product, e.g., magnesium carboxylate, from thefermentation broth, before, after, or simultaneous with biomass removal,and optionally subjecting the magnesium carboxylate to a washing step.

Depending on the carboxylic acid produced, another intermediate step maybe subjecting the fermentation broth to a concentration step to increasethe concentration of magnesium carboxylate in the composition beforeacidification. This step may be carried out before, after, orsimultaneous with biomass removal.

Other intermediate steps, e.g., purification steps, may be carried outas desired, as will be evident to the skilled person.

The next step in the integrated process according to the invention issubjecting the magnesium carboxylate to an acidification step, alsosometimes indicated as acidulation step, wherein the magnesiumcarboxylate is contacted with HCl in an aqueous environment to form anaqueous mixture comprising carboxylic acid and magnesium chloride. Thereare various ways in which this step can be effected. The acidulationstep is typically conducted by bringing the carboxylate salt in contactwith an acidic HCl solution. However, in some embodiments it may also bepossible to contact the carboxylate salt with gaseous HCl.

The carboxylate salt may be in solid and/or dissolved form. In oneembodiment, the carboxylate salt is provided in solid form. In thiscase, the acidulation step is conducted by bringing the carboxylate saltin contact with an acidic solution. The advantage of preparing theaqueous mixture from carboxylate salt in solid form is that very highcarboxylic acid concentration can thus be obtained, such asconcentration of at least 15 wt. %, in particular at least 25%, up to,e.g. 50 wt. %, or e.g. 40 wt. %.

The carboxylate salt may also be in dissolved form, typically as part ofan aqueous solution. In this case, the acidulation step can be conductedby bringing the carboxylate salt in contact with an acidic solution oran acidic gas.

The acidulation step may also be conducted on a mixture of carboxylicacid and carboxylate salt. Such a mixture may for example be obtained ina low pH fermentation. The mixture may for example be an aqueoussuspension.

When acidulation of the carboxylate salt is conducted by contacting itwith an acidic HCl solution, it preferably has an acid concentration ashigh as possible. Such a high acid concentration will result in anaqueous mixture with a high carboxylic acid concentration, which isdesirable. The acidic solution therefore comprises at least 5 wt. %,more preferably at least 10 wt. % and even more preferably at least 20wt. % acid, based on the total weight of the acidic solution.

Acidulation is typically conducted using an excess of acid. The excessis preferably small, such that the aqueous mixture obtained is nothighly acidic, which may not be desirable in view of further processingsuch a mixture. For example, the excess of acid used may be such thatthe resulting aqueous mixture has a pH 2 or lower, preferably a pH of0-1.

In case gaseous HCl is used, it may be contacted by bringing it incontact with a carboxylate solution or suspension. In particular, HClgas may be blown through the solution or suspension.

Preferably, acidulation is conducted at a temperature of 75° C. or less.At higher temperatures, it becomes uneconomical to adapt equipment tothe harsh conditions of an acidic environment at high temperatures.

The acidification step results in the formation of an aqueous liquidcomprising carboxylic acid and magnesium chloride. This aqueous liquidis subjected to a separation step, optionally after intermediateprocessing steps have been carried out such as a concentration step.

Suitable separation steps are known in the art. The nature of the stepto be used depends on the nature and property of the acids.

Where the carboxylic acid is present in whole or in part as solid in theaqueous liquid, separation can take place using conventionalsolid-liquid separation methods such as filtration, centrifugation, etc.

Where the carboxylic acid is present in whole or in part as a separateorganic phase in the aqueous liquid, separation can take place usingconventional liquid-liquid separation methods, e.g., decantation,settling, centrifugation, use of plate separators, use of coalescers,and use of hydrocyclones. An extractant may be added to improve theseparation efficiency. Combination of different methods and apparatusmay also be used.

Where the carboxylic acid is present dissolved in the aqueous liquid,separation can take place using, e.g., extraction with a suitableextractant.

The nature of the carboxylic acid manufactured is not critical to theintegrated process according to the invention.

In one embodiment the carboxylic acid is a mono-, di- or tri-carboxylicacid comprising at least 2, but no more than 6 carbon atoms (C2-6carboxylic acid). In one embodiment, the carboxylic acid is selectedfrom the group consisting of lactic acid, succinic acid, propionic acid,3-hydroxypropionic acid, 2-, 3-, and 4-hydroxybutyric acid, citric acid,fumaric acid, itaconic acid, adipic acid, acrylic acid, levulinic acid,maleic acid, 2,5-furandicarboxylic acid, mandelic acid, malic acid, andtartartic acid. Preferably, the carboxylic acid is selected from thegroup consisting of lactic acid, succinic acid, propionic acid,3-hydroxypropionic acid, 2-, 3-, and 4-hydroxybutyric acid and citricacid.

In one embodiment, the carboxylic acid is selected from themono-carboxylic acids with 2-6 carbon atoms. In one embodiment, themonocarboxylic acid with 2-6 carbon atoms does not containhydroxyl-groups. Within this group, examples of suitable acids arepropionic acid, acrylic acid, butyric acid, and valeric acid.

In another embodiment, the monocarboxylic acid contains at least onehydroxyl-group. Within this group, in one embodiment it may be preferredto select the acid from the group of lactic acid, glycolic acid,3-hydroxypropionic acid, 2-, 3-, and 4-hydroxybutyric acid. In anotherembodiment within this group it may be preferred to select the acid fromthe group of glycolic acid, 3-hydroxypropionic acid, and 2-, 3-, and4-hydroxybutyric acid. In a further embodiment it may be preferred forthe acid to be lactic acid.

In another embodiment, the carboxylic acid is a polycarboxylic acid,more in particular a di- or tri-carboxylic acid comprising at least 2,but no more than 6 carbon atoms (C2-6 carboxylic acid). In oneembodiment, the polycarboxylic acid is selected from the groupconsisting of succinic acid, citric acid, fumaric acid, itaconic acid,adipic acid, maleic acid, 2,5-furandicarboxylic acid, mandelic acid,malic acid, and tartartic acid. Preferably, the polycarboxylic acid isselected from the group consisting of succinic acid, citric acid,fumaric acid, itaconic acid, adipic acid, and 2,5-furandicarboxylicacid. The polycarboxylic acid may in particular be selected fromsuccinic acid, fumaric acid, itaconic acid, and 2,5-furandicarboxylicacid.

FIG. 3 illustrates an embodiment of the integrated process according tothe invention. In FIG. 3, a fermentation step is carried out infermentation reactor (101), which is provided with a carbon source andoptionally further components such as nutrients through lines not shown.In the fermentation step a carbon source is fermented by means of amicro-organism in a fermentation broth to form carboxylic acid andneutralizing at least part of the carboxylic acid by adding a magnesiumbase, thereby obtaining a magnesium carboxylate. The magnesium base isadded through line (3). The magnesium base is derived from MgO generatedin the thermal decomposition step. The MgO may be provided as such, orafter having been slurried in an aqueous liquid or converted tomagnesium hydroxide in steps not shown. The fermentation brothcomprising a magnesium carboxylate salt is provided to an acidificationstep (103) through line (102). Intermediate steps such as biomassremoval or concentration may be carried out, but are not shown. In theacidification step (103) the magnesium carboxylate is contacted with HClin an aqueous environment to form an aqueous mixture comprisingcarboxylic acid and magnesium chloride. The HCl is provided through line(10) and is derived from the drying step (7). In the embodimentpresented in FIG. 3, the HCl-containing gas stream derived from dryer(7) is provided through line (8) to an absorber (9), where the HCl isadsorbed in water to form a HCl solution, which is provided through line(10) to the acidification step (103). It is also possible to provide theHCl-containing gas stream (8) directly to acidification step (103).

The aqueous mixture comprising carboxylic acid and magnesium chloride isprovided to a separation step (105) through line (104). The separationstep may be carried out as described above. Where separation step (105)makes use of an extractant, this is provided through lines not shown.Separation step (105) results in an effluent comprising carboxylic acidand a magnesium chloride solution. The product carboxylic acid iswithdrawn through line (106). The magnesium chloride solution iswithdrawn through line (6), and processed further as described above inthe context of FIG. 2).

As will be evident to the skilled person, the various aspects of thethermohydrolysis step are also applicable where this step isincorporated into a process for conversion of a magnesium chloridesolution. The various aspects of the process for conversion of amagnesium chloride solution are also applicable where this process isincorporated into an integrated fermentation process.

The present invention is elucidated by the following examples, withoutbeing limited thereto or thereby.

EXAMPLES

Starting materials were prepared as follows:

MgCl₂.6H₂O: Magnesium chloride hexahydrate was obtained commercially.MgCl₂.4H₂O: Magnesium chloride tetrahydrate was obtained by placingmagnesium chloride hexahydrate in an oven at 130° C. for 24 hours. Theweight reduction of the sample was measured, confirming the formation ofmagnesium chloride tetrahydrate.MgCl₂.2H₂O: Magnesium chloride dihydrate was created by spray-drying amagnesium chloride solution at 140° C. TGA measurements confirmed thatthe magnesium chloride compound contained at least 80 wt. % of magnesiumchloride dihydrate.MgCl2: Anhydrous magnesium chloride was obtained commercially.

The samples were tested as follows:

A small amount of solid material is placed in a quartz glass cruciblewith a porous metal disc as base. The arrangement of material in thecontainer with the porous metal base in placed in a glass tube connectedto a burner. Using a suction pump hot gases from the burner aredisplaced through the sample. A temperature sensor is placed inside thesample to record the temperature, and the temperature is controlled bycontrolling the flow delivered by the suction pump.

For each material a set of experiments was carried out at 500° C. and600° C. Samples were taken after specified periods of time, and theconversion into magnesium oxide determined. The results are presented intables 1 and 2.

TABLE 1 Thermal decomposition at 500° C. - degree of conversion Time(minutes) Species 2 5 10 15 MgCl₂•6H₂O Melts MgCl₂•4H₂O 0.3 0.8 0.8 0.8MgCl₂•2H₂O 0.4 0.4 0.4 0.4 MgCl₂ 0 0 0 0

TABLE 2 Thermal decomposition at 600° C. - degree conversion Time(minutes) Species 2 5 10 15 MgCl₂•6H₂O Melts MgCl₂•4H₂O 0.95 1 1 1MgCl₂•2H₂O 0.9 0.95 0.95 0.95 MgCl₂ 0.15 0.15 0.15 0.15

As can be seen from the above tables, MgCl₂.6H₂O melts, both at 500° C.and at 600° C. MgCl₂ does not show any conversion into MgO under thesereaction conditions in this time frame. MgCl₂.4H₂O and MgCl₂.2H₂O bothshow substantial conversion into MgO. At 500° C. MgCl₂.4H₂O shows aconversion of 80% after 10 minutes, and at 600° C., a conversion of 95%is already obtained after 2 minutes, with 100% conversion being obtainedafter 5 minutes. For MgCl₂.2H₂O the conversion is slower, both at 500°C. and at 600° C. This illustrates that MgCl₂.4H₂O shows fasterconversion at lower reaction temperatures than MgCl₂.2H₂O.

1. Method for conversion of magnesium chloride into magnesium oxide andHCl, comprising: providing a magnesium chloride compound to athermohydrolysis reactor, the reactor being at a temperature of at least300° C. but below 1000° C.; and, withdrawing MgO from thethermohydrolysis reactor in solid form, and withdrawing an HClcontaining gas stream from the thermohydrolysis reactor; wherein themagnesium chloride compound provided to the thermohydrolysis reactor isa solid magnesium chloride compound which comprises at least 50 wt. % ofMgCl₂.4H₂O and which comprises less than 40 wt. % of the total ofmagnesium chloride anhydrate, magnesium chloride monohydrate, andmagnesium chloride dihydrate.
 2. The method according to claim 1,wherein the magnesium chloride compound comprises less than 30 wt. % ofmagnesium chloride hexahydrate.
 3. The method according to claim 1,wherein the magnesium chloride compound comprises less than 30 wt. % ofthe total of magnesium chloride anhydrate, magnesium chloridemonohydrate and magnesium chloride dihydrate.
 4. The method according toclaim 1, wherein the magnesium chloride compound comprises less than 30wt. % of magnesium chloride hexahydrate and less than 30 wt. % of thetotal of magnesium chloride anhydrate, magnesium chloride monohydrateand magnesium chloride dihydrate.
 5. The method according to claim 1,wherein at least 60 wt. % the magnesium chloride compound is MgCl₂.4H₂O.6. The method according to claim 1, wherein the thermohydrolysis reactoris at a temperature below 800° C.
 7. The method according to claim 1,wherein the thermohydrolysis is carried out in the presence of a gasstream.
 8. The method according to claim 1 further comprising:subjecting a magnesium chloride solution to drying at a temperature of100-160° C. to form the magnesium chloride compound comprising at least50 wt. % of MgCl₂.4H₂O and less than 40 wt. % of the total of magnesiumchloride anhydrate, magnesium chloride monohydrate, and magnesiumchloride dihydrate.
 9. The method according to claim 8, wherein thedrying is performed by spray-drying.
 10. The method according to claim8, wherein the drying is carried out in the presence of HCl.
 11. Themethod according to claim 10 further comprising providing the HClcontaining gas stream from the thermohydrolysis reactor to the drying.12. The method according to claim 1 further comprising: subjecting acarbon source to a fermentation to form a carboxylic acid, whichfermentation comprises fermenting a carbon source by means of amicro-organism in a fermentation broth to form carboxylic acid andneutralizing at least part of the carboxylic acid by adding a magnesiumbase selected from magnesium oxide and magnesium hydroxide, therebyobtaining a magnesium carboxylate; subjecting the magnesium carboxylateto an acidification wherein the magnesium carboxylate is contacted withHCl in an aqueous environment to form an aqueous mixture comprisingcarboxylic acid and magnesium chloride; and separating the carboxylicacid and magnesium chloride from the aqueous mixture; wherein themagnesium chloride forms the magnesium chloride compound provided to thethermohydrolysis reactor.
 13. The method according to claim 12, whereinthe obtained carboxylic acid is selected from the group consisting ofmono, di- and tricarboxylic acids having at least two but no more than 6carbon atoms (C2-C6 carboxylic acid).
 14. The method according to claim12, wherein the obtained carboxylic acid is selected from the groupconsisting of: lactic acid; succinic acid; propionic acid;3-hydroxypropionic acid; 2-, 3-, and 4-hydroxybutyric acid; citric acid;fumaric acid; itaconic acid; adipic acid; acrylic acid; levulinic acid;maleic acid; 2,5-furandicarboxylic acid; mandelic acid; malic acid; and,tartaric acid.
 15. The method according to claim 12, wherein theacidification comprises either bringing the magnesium carboxylate insolid form, suspension or solution into contact with an aqueous HClsolution or bringing a magnesium carboxylate solution or suspension intocontact with HCl gas.
 16. The method according to claim 12 furthercomprising recycling the magnesium oxide withdrawn from thethermohydrolysis reactor at least in part to the fermentation.
 17. Themethod according to claim 1 further comprising: subjecting a carbonsource to a fermentation to form a carboxylic acid, which fermentationcomprises fermenting a carbon source by means of a micro-organism in afermentation broth to form carboxylic acid and neutralizing at leastpart of the carboxylic acid by adding a magnesium base selected frommagnesium oxide and magnesium hydroxide, thereby obtaining a magnesiumcarboxylate; subjecting the magnesium carboxylate to an acidificationwherein the magnesium carboxylate is contacted with HCl in an aqueousenvironment to form an aqueous mixture comprising carboxylic acid andmagnesium chloride; subjecting the aqueous mixture comprising carboxylicacid and magnesium chloride to a separation, to form an effluentcomprising carboxylic acid and a magnesium chloride solution; andsubjecting the magnesium chloride solution to drying at a temperature of100-160° C., which drying forms the magnesium chloride compoundcomprising at least 50 wt. % of MgCl₂.4H₂O and comprising less than 40wt. % of the total of magnesium chloride anhydrate, magnesium chloridemonohydrate, and magnesium chloride dihydrate.
 18. The method accordingto claim 17, wherein the obtained carboxylic acid is selected from thegroup consisting of mono, di- and tricarboxylic acids having at leasttwo but no more than 6 carbon atoms (C2-C6 carboxylic acid).
 19. Themethod according to claim 17, wherein the obtained carboxylic acid isselected from the group consisting of: lactic acid; succinic acid;propionic acid; 3-hydroxypropionic acid; 2-, 3-, and 4-hydroxybutyricacid; citric acid; fumaric acid; itaconic acid; adipic acid; acrylicacid; levulinic acid; maleic acid; 2,5-furandicarboxylic acid; mandelicacid; malic acid; and, tartaric acid.
 20. The method according to claim17, wherein the acidification comprises either bringing the magnesiumcarboxylate in solid form, suspension or solution into contact with anaqueous HCl solution or bringing a magnesium carboxylate solution orsuspension into contact with HCl gas.
 21. The method according to claim17, wherein the drying is performed by spray-drying.
 22. The methodaccording to claim 17, wherein the HCl-containing gas stream derivedfrom the thermohydrolysis reactor is provided to the drying.
 23. Themethod according to claim 17 further comprising recycling theHCl-containing gas stream derived from the drying at least in part tothe acidification.
 24. The method according to claim 17 comprisingrecycling the magnesium oxide withdrawn from the thermohydrolysisreactor at least in part to the fermentation.
 25. The method accordingto claim 1 for further obtaining a carboxylic acid, the methodcomprising: subjecting a carbon source to a fermentation to form acarboxylic acid, which fermentation comprises fermenting a carbon sourceby means of a micro-organism in a fermentation broth to form carboxylicacid and neutralizing at least part of the carboxylic acid by adding amagnesium base selected from magnesium oxide and magnesium hydroxide,thereby obtaining a magnesium carboxylate; subjecting the magnesiumcarboxylate to an acidification wherein the magnesium carboxylate iscontacted with HCl in an aqueous environment to form an aqueous mixturecomprising carboxylic acid and magnesium chloride; and separating themagnesium chloride and a product stream of the carboxylic acid from theaqueous mixture; wherein the magnesium chloride forms the magnesiumchloride compound provided to the thermohydrolysis reactor.
 26. Themethod according to claim 25, wherein the obtained carboxylic acid isselected from the group consisting of mono, di- and tricarboxylic acidshaving at least two but no more than 6 carbon atoms (C2-C6 carboxylicacid).
 27. The method according to claim 25, wherein the obtainedcarboxylic acid is selected from the group consisting of: lactic acid;succinic acid; propionic acid; 3-hydroxypropionic acid; 2-, 3-, and4-hydroxybutyric acid; citric acid; fumaric acid; itaconic acid; adipicacid; acrylic acid; levulinic acid; maleic acid; 2,5-furandicarboxylicacid; mandelic acid; malic acid; and, tartaric acid.
 28. The methodaccording to claim 25, wherein the acidification comprises eitherbringing the magnesium carboxylate in solid form, suspension or solutioninto contact with an aqueous HCl solution or bringing a magnesiumcarboxylate solution or suspension into contact with HCl gas.
 29. Themethod according to claim 25 comprising recycling the magnesium oxidewithdrawn from the thermohydrolysis reactor at least in part to thefermentation.
 30. The method as defined in claim 1 for further obtaininga carboxylic acid, the method comprising: subjecting a carbon source toa fermentation to form a carboxylic acid, which fermentation comprisesfermenting a carbon source by means of a micro-organism in afermentation broth to form carboxylic acid and neutralizing at leastpart of the carboxylic acid by adding a magnesium base selected frommagnesium oxide and magnesium hydroxide, thereby obtaining a magnesiumcarboxylate; subjecting the magnesium carboxylate to an acidificationwherein the magnesium carboxylate is contacted with HCl in an aqueousenvironment to form an aqueous mixture comprising carboxylic acid andmagnesium chloride; subjecting the aqueous mixture comprising carboxylicacid and magnesium chloride to a separation, to form a magnesiumchloride solution and a product stream being an effluent comprisingcarboxylic acid; and subjecting the magnesium chloride solution todrying at a temperature of 100-160° C., which drying forms the magnesiumchloride compound comprising at least 50 wt. % of MgCl₂.4H₂O andcomprising less than 40 wt. % of the total of magnesium chlorideanhydrate, magnesium chloride monohydrate, and magnesium chloridedihydrate.
 31. The method according to claim 30, wherein the obtainedcarboxylic acid is selected from the group consisting of mono, di- andtricarboxylic acids having at least two but no more than 6 carbon atoms(C2-C6 carboxylic acid).
 32. The method according to claim 30, whereinthe obtained carboxylic acid is selected from the group consisting of:lactic acid; succinic acid; propionic acid; 3-hydroxypropionic acid; 2-,3-, and 4-hydroxybutyric acid; citric acid; fumaric acid; itaconic acid;adipic acid; acrylic acid; levulinic acid; maleic acid;2,5-furandicarboxylic acid; mandelic acid; malic acid; and, tartaricacid.
 33. The method according to claim 30, wherein the acidificationcomprises either bringing the magnesium carboxylate in solid form,suspension or solution into contact with an aqueous HCl solution orbringing a magnesium carboxylate solution or suspension into contactwith HCl gas.
 34. The method according to claim 30, wherein the dryingis performed by spray-drying.
 35. The method according to claim 30,wherein the HCl-containing gas stream derived from the thermohydrolysisreactor is provided to the drying.
 36. The method according to claim 35comprising recycling the HCl-containing gas stream derived from thedrying at least in part to the acidification.
 37. The method accordingto claim 30 comprising recycling the magnesium oxide withdrawn from thethermohydrolysis reactor at least in part to the fermentation.
 38. Themethod according to claim 1 characterized by a residence time,calculated from the provision of the magnesium chloride compound to thethermohydrolysis reactor to the removal of the corresponding magnesiumoxide from the reactor, of at most 30 minutes.